Ethers of hydroxyalkyl amine bases, their salts, and quaternary ammonium compounds



Patented Sept. 29, 1942 amass F nrnaoxramn. Amma msas, 'rrmm SALTS, m oua'ranmar AM- MONIUM COIiflOUNDS Richard Hnttenlocher, Greil, Thuring'en, Ger

many; vested in the Alien Property Custodian No Drawing. Application January 29, 1938, Se-

rial No. 187,749. In Germany February 3,

3 Claims.

This invention relates to the production of alkyl ethers of hydroxyalkyl amine bases, of salts and quaternary ammonium compounds of these alkyl ethers as well as to the use'of these alkyl ethers asa textile improvement agent, especially for avivageand softening, for improving cellulose wool or similar fibres as regards their fitness of being spun, for delusterizing fabrics and fibres and for making emulsions having a high affinity to animal, vegetable and artificial fibres and fabrics.

' It is known to react hydroxyalkyl amines with ethylene oxide or with propylene oxide to produce the corresponding glycol ethers of the hydroxyalkyl amine bases. Heretofore, however, it had not been possible to bring about a reaction between hydroxyalkyl amine bases with alkyl halogenides or with alkyl sulphates and to etherify the hydroxyl group. Especially alkylating with higher molecular aliphatic or cyclo-aliphatic compounds oilers considerable difliculties. The general mode of producing ethers which consists in converting alcohols with alkaline metals into the alcoholates andthereupon converting the latter with alkyl or aralkyl halogenides into the desired ethers cannot be immediately transferred to the alkylating of hydroxyalkyl amine bases.

If one "moi of alkaline metal is reacted with one mol of anhydroxyalkyl amine base, the reaction mass will solidify as soon as somewhat more than one half of the alkaline metal is added; by this naturally the further reaction between the alkaline metal and the hydroxyalkyl bases will be rendered impossible.

If it be attempted to forcibly effect the quantitative conversion by an increase in temperature, the hydroxyalkyl base will undergo polymerisation. There will be produced dark brown resinous polymerisation products causing a loss of valuable hydroxyalkyl amine bases resulting in decreased yields and impurities in the final products.

Nor can these difllculties be avoided by addition of solvents. Besides, the high boiling solvents necessary on account of the high reaction temperatures can be removed from the final products only with diificulty and rather firmly adhere to the latter.

Now, I have found, that these drawbacks may easily be obviated by causing the reaction to be solved, one quarter of the alkyl chloriderequired for the etherifying is added and caused to undergo reaction. Thereupon again one quarter of the required alkaline metal is supplied to the reaction mass, and one quarterof the alkyl chloride required again added by stirring, subsequent to dis- I (cnlpon In this formula R and R represent either H- atoms or alkyl groups or their derivatives or hydroxyalkyl groups, while a: signifies a whole number. Thus, for instance, mono-, di-, or trioxy ethyl amine, mono-, di-, or trioxypropyl amine as well as the corresponding higher molecular oxamines and the corresponding iso-forms of these compounds may be employed. In the monoand dioxyalkylamines the- H-atoms adhering to the nitrogen may be replaced by any other alkyl radicals, such as for instance methyl,

ethyl, propyl, butyl, pentyl, hexyl, heptyl, hexadecyl radicals and eventually by substitutes thereof. i urthermore, as hydroxyalkyl amines also the derivatives of the diamines may be employed, for instance, the oxyethyl ethylene diamine and furthermore the dioxyethyh, trioxyethyland the tetraoxyethyl-compound of the ethylene diamine.

As alkyl chlorides according to my invention there are used compounds having the formula R. X, in which R signifies an alkyl, cycloalkyl or aralkyl radical comprising at. least four carbon atoms, and X any halogen, especially chlorine, bromine or iodine. Thus, for instance, butyl chloride, cetyl chloride, cyclobutyl chloride, cyclopentyl chloride, cyclohexyl chloride, benzyl chloride, phenyl ethyl chloride, and furthermore polynuclear aralkyl derivatives, such as for instance the i-ethyl chloride-3-octyl naphthaline, may be used.

In the hydroxyalkyl amine bases which contain two or three hydroxyalkyl residues by the etherifying according to the invention one, two or hydroxyl groups may be alkylated.

The high molecular alkyl ethers of hydroxyalkyl amine bases made according to my invention are practically non-saponifiable and will impart an extraordinarily soft and smooth touch three to text es, far superior to that obtainable by the com unds otherwise used for this purpose.

The alkyl ethers of hydroxyalkyl amine bases may be converted for technical purposes especially in order to increase their solubility in water, bytreatment with acids into salts. More especially, they may be used in the form of acetates, formiates or lactates.

The high molecular alkyl ethers, of the hydroxyalkyl amine bases may furthermore be used in the form of quaternary ammonium com-- alkyl amines or their salts and their quaternary ammonium compounds are possessed of extraordinarily effective softening and aviving properties. They may, therefore, advantageously be used as aviving and softening agents for textiles, especially for threads, fibres and fabrics consisting of regenerated cellulose. Thus, for instance, the touch presented by cuprated silk which had been treated in the form'of a rope with 2 g. of dicetyl ether of the triethanolamine is better than the touch presented by the same silk which had been avived with 4 g. of dipalmitic-ester of the triethanolamine under the same conditions.

The newaviving agents are also possessed of such a substantive effectiveness that a bath containing from 0.2 to 0.5 g. ofthe new aviving agent per liter after treatment of artificial silk fabrics therein will practically be fully extracted. In spite of the low concentration of high-molecular alkyl ether of hydroxyalkyl amines or their salts will be deposited on the rayon fibres.

In view of the large quantities of softening agents which must be used, both in the rayon and in the cellulose wool industry, as well as in improvement plants for rayon textiles or fabrics, the increased eflect of the high-molecular alkyl ethers of hydroxyalkyl amine bases constitutes a remarkable progress, as with one half and washed is treated in a bath comprising highmolecular ethers of hydroxyalkyl amine bases or their salts or quaternary ammonium compounds. The above mentioned high-molecular ethers of hydroxyalkyl amine bases are possessed of the remarkable property to prevent or counteract the aforesaid sticking together of the threads so that several threads adhering to each other may easily be separated after such treatment and do not present any reluctance to the subsequent mechanical treatment during I carding or combing to which they are subjected of the heretofore necessary quantities high-grade results may be attained consisting particularly in great savings-of fatty materials.

In addition I have found that with the aid of the high-molecular alkyl ethers of hydroxyalkyl amine bases, their salts and their quaternary ammonium compounds it will be-possible to extensively improve the manufacture of cellulose wool and similar fibres from regenerated cellulose. In the manufacture of such fibres, as

known, it is never quite possible to avoid sticking together of the several capillary threads after passing out of the cellulose solutions and out of the spinning nozzles or spouts. This sticking together of the several threads constitutes a great drawback considerably impairing the fabrics made from artificial fibres of small length as regards their fitness for the spinning process. Surprisingly, now I have found that it-wi1l be in accordance with the use for which the cellulose wool is intended.

The cellulose .wools so-treated, therefore, will furnish faultness, fabrics and the waste products which have been rather considerable during spinning or comblngmay be reduced to a minimum.

Thus, for instance, cellulose wool made from viscose, spun by means of spinning nozzles having-about 3,000 apertures, precipitated, desul- Dhurized and washed may be treated according to my invention in a bath comprising per liter 2.0 g. of a formiate of the dicetyl ether of the triethanol amine at 60. C. The cellulose wool remains for about 15 minutes in the warm bath and is thereupon centrifuged and dried. By this treatment the sticking property of the cellulose wool-will be decreased 75% as compared with a normal treatment by means of the usual oil emulsions.

This treatment with the high-molecular ethers of hydroxyalkyl amine bases or their salts or their quarternary ammonium compounds will'at the same time impart a high degree of softness to the cellulose wool. Eventually further materials may be added to the treatment baths, such as for instance albuminous substances, hydrocarbons,

' soaps, sulfonated fatty substances, and similar substances. These added substances depend upon the purpose or use for which the respective cellulose wool is destined.

Furthermore, high-molecular ethers of hy- I droxyalkyl amine bases, their salts .or their quaternary ammonium compounds containing one or more hydroxyl groups are advantageously suited to delusterize the lustre of fabrics such as silk rayon, cellulose wool and the like by means of pigments. By employing high-molecular ethers-of hydroxyalkyl amines, their salts or quatemary/ ammonium compounds containing one or more free hydroxyl groups in the molecule, pigments of all kinds may be uniformly and easily applied to all kinds of textile fibres. The high-molecular ethersof hydroxyalkyl amine bases are possessed of high affinity with respect to textile fibres of all kinds and cause the pigments which together with said ethers are driven onto the fabric to adhere thereto with extraordinary firmness. With these substances there may be attained delustrings of such uniformity and permanence as can otherwise be produced only with dlfliculty by means ,of a treatment in two baths.

The higher molecular alkyl ethers of the hydroxyalkylaminebasesaswellastheirsaltsand possible to considerably prevent the aforementioned sticking together of the threads, if the cellulose wool subsequently to being-precipitated quarternary ammonium compounds also represent valuable emulgents which may be used for the production of emulsions having a high degree of amnity with respect to animal, vegetable.

and artificial fibres and fabrics, The heretofore known emulsions which were made by the aid of the usual protective colloids do not present any appreciable amnity with respect to animal, vegedroxyalkyl amine bases, their salts or their, quaternary ammonium compounds it will be possible to emulsify in water aliphatic, cyclo-aliphatic, aromatic and hydroaromatic hydrocarbons, alcohols, aldehydes and ketones, fats, waxes and resins as" well as their acids and insoluble salts, artificial resins and similar substances that are difficultly soluble or insoluble in water. These aqueous emulsions present a high degree of atfinity with respect to animal, vegetable and artificial fibres and substances and,- accordingly, may be employed with advantage in such cases where fibres, fabrics, artificial masses, leather and the like are to be treated with emulsions of the aforementioned substances.

The progress attained by employing these emulsions consists therein that treatment baths containing per liter of from 1 to 5 g. of the emulsions made in accordance with my invention will have the same or frequently still a higher efi'ect than that which may be attained with treatment baths containing the ordinary heretofore known emulsions in an amount of 50 g. and more per litre.

Examples 1. Within a reflux apparatus there are added to 150 parts by weight of triethanol amine at a temperature of 105 C. under strong stirring at first parts by weight of sodium in small portions; Upon complete conversion of the sodium the mass is cooled down to 75 C., 40 parts by weight of butyl chloride are slowly added, and heat is applied for such a length of time until the temperature has again increased to 105 C. and until in the refiux cooler no further condensation of butyl chloride is observed. Thereupon there are added 36 parts by weight of sodium, likewise in small portions, and 150 parts by weight of butyl chloride in three portions both under strong stirring. After removal of the formed common salt there will be obtained a quantitative yield of the produced dibutyl ether of the triethanol amine. This product represents a white oily liquid which cannot be distilled without decomposing.

2. To 150 parts by weight of triethanol amine there are added under stirring at 105 C. at first 10 parts by weight of sodium in small portions. Upon complete conversion of this mass there are slowly added at the same temperature 110 parts by weight of cetyl chloride which is left to condense for some length of time. Thereupon the addition .of sodium in small portions is continued by further adding 13 parts'by weight of sodium; at the same time there are added 150 parts by weight of cetyl chloride, the temperature besalt is removed and the formed dicetyl ether of the triethanol amine will be obtained in a quantitative yield. This product consists of a yellowish fatlike substance with a melting point at 28.5 it. (31:15 corrected). The refraction index nn'-' is 3. To 343 parts of hexadecyl oxyethyl oxypropyl amine having-the formula:

uHI NCH2CHIOH CHzCHtCHrOH are added under intensive stirring 10 parts of potassium at a temperature of 105 C., said potassium being pressed in melted condition and in small portions into the reaction mass. Upon complete conversion there are slowly added 38 parts of cyclo-pentyl bromide at 105 C. and heated for such a length of time until the reaction is completed. Thereupon again 20 parts of potassium are added and converted with 75 parts of cyclopentyl bromide. Now again 10 parts of potassium are added and subsequent thereto 38 parts of cyclo-pentyl bromide. The reaction mass is separated after completion of the reaction from the formed potassium bromide by filtration, thus obtaining the desired cyclo-pentyl ether in a practically quantitative yield and with a high degree of purity.

4. By conversion of one mol of ethylene chlorhydrine with one mol of dicetyl ether of the trioxyethyl amine there is obtained a quantitative yield of the dicetyl ether of the tetraethanol ammonium chloride. This compound is a yellowish substance of greasy consistency which when dissolved in water will produce milky emulsions. The refraction index n is 1.4444. Melting point C. (not corrected).

From this quaternary base or its chloride a solution of l g. per liter is sprayed onto ropes of ing maintained at from to C. Now fur- I -260 parts by weight of cetyl chloride are added,

the temperature raised up to from to C.

-and the condensation completed. The common 75 together of the threads and may easily and prop-v erly be carded and spun.

5. One mol of mono-chloracetic cetyl ester is heated together with the equimolar amount of didodecyl ether of the trioxyethyl amine for 8 hours on the water bath. The so formed quaternary compound consists of a fatlike product which will furnish permanent solutions, especially by addition of small amounts of formic acid, .when dissolved in aqueous solutions. These permanent solutions are possessed of a high degree of aifinity with respect to animal, vegetable and artificial fibrous materials and are excellently suitable to suppress the sticking together of the threads of cellulose wool. t

6. Equimolar amounts of dicetyl ether of the trioxyethyl amine and CGtYI-a-ChlOllllBthYl ether are condensed with each other at atemperature between '70 and 80 C. for a length of time until.

conversion into the quaternary ammonium compound has taken place. Thereaction product may be used for the making of emulsions. It is also suited forthe-delusterizing of the lustre of artificial silk by means of pigments.

8. Stockings consisting of rayon made from viscose are treated subsequent to dyeing for 15 to 20 minutes in a bath at-a temperature between 35 and 40 C., said bath containing 0.2 g. of the dioctadecyl ether of the triethanol amine formiate and 0.8 g. of titanium dioxide per liter of the treatment bath. Upon completion of the delusterizing the stockings are thoroughly washed in cold water, dried and thereupon treated'in the finishing machine. The material thus obtained is delusterized and the pigment adheres to such an extent to the stockings that also during treatment in the finishing machine there no blurs or stripes will appear on the fabric.

9. Woven goods consisting of 80% of cellulose wool and 20% cotton are treated on the reel in a bath at a temperature of 40 0., said bath-containing 0.3 g. dichloroleyl ether of the triethanol amine in form of the tartrate and 1 g. of zinc suliide. The goods are kept running on the reel for about half an hour, thereupon they are washed in cold water, centrifuged and carried to the dry ing machine. The fabric is of cottonlike appearance.

10. Stockings of natural silk are treated with an aqueous bath containing per litre 0.1 g. of

dicetyl ether of the triethanol amine-acetate and 0.5 g. of China clay for a quarter of an hour at a temperature of 30 C. The stockings'when so treated will be given the dull lustre desired according to the present fashion.

11. Woven rayon fabric are sprayed subsequent to dyeing with an aqueous solution containing per liter 2 g. of dilauryl ether of the triethanol amine formiate, 2 g. of titanium dioxide and 2 g. ZnS. Subsequent to the spraying the fabrics are dried on the stretching frame and furthermore treated on the felt calender.

12. 20 parts of the dioctadecenyl etherof the trioxytriethyl amine acetate are mixed with 60 .parts of vaseline oil for the production of a reeling oil. Now a bath is made containing 3 g. of this mixture per liter of the bath and freshly spun rayon treated with this solution. Rayon prepared in this way may be conveniently reeled.

13. 30 parts of dioctadecyr ether of the trioxytrietlrvl amine formiate are melted together with 50 parts of parafllne (fusion point 50/55). With the aid of this product emulsions can be made containing 3 g. per liter of the bath and ropes of freshly spun cellulose wool treated with these aqueous emulsions at a temperature between 60 and 75 C. The heavily swollen-up ropes of cellulose wool quickly absorb the whole of the emulsified substances, and are thereupon cut and dried. Cellulose wool treated in this way is repulsive to water and possessed of greatly reduced water absorbing properties, and therewith also of diminished swelling properties.

l4. 5 g. of aluminium formiate solution of 13 36. are added to an emulsion prepared in accordance with Example 13, per liter of the bath and half-woolen fabrics treated-in this bath. The fabrics will be water-proof after being dried and no spots will be formed thereon due to water.

15. Form parts of dihexadecyl' ether of the trioxytriethyl amine forminate and 40 parts of a solution of soja lecithin in soja oil a homogeneous mixture is made at a temperature of 40 C.

From this product there is made an aqueous emulsion containing 1 g. of effective substance per liter of the bath. In this bath now woven rayon goods are avived subsequent to dyeing. The emulsified substances are almost completely absorbed and the rayon goods will present a pleasing 'soft touch.

16. From 20 parts of dodecyl ether of the diarydiethyl amine forminate and 60 parts of sharkoil there is prepared a solution at a temperature of 60 c. An aqueous emulsion containiiitsg. of this mixture is used for fattening chrome tanned leather. As early as after 10 minutes the liquors in the barrel will be clear and the fat completely absorbed by the leather. I 17. From 20 parts of dodecyl ether of the dioxydiethyl amine acetate and 80 parts of hydrated marine animal oils there is prepared a deliquescent. Aqueous emulsions of this mixture may be used for the fattening of cotton for vigogne spinning or as an addition to warp sizing agents.

18. From 10 parts of dodecyl ether of the dioxydiethyl amine acetate and 40 parts of earthnut oilthere is prepared a solution. Aqueous emulsions of this solution may be used for the softening or worsted yarns.

I claim:

1. A process which comprises reacting a hydroxyalkyl amine base of the general formula wherein R and R represent a substituent selected from the group consisting of hydrogen, alkyl radicals, and hydroxyalkyl radicals, while :n represents a whole number, with an alkali metal and subsequently with an organic halide selected from the group consisting of alkyl halides contaming at least four carbon atoms in the molecule, cycloalkylhalides and aralkyl halides, the reaction with the alkali metal and with the organic halide being effected in at least two steps using for each step a part of the stoichiometric quantity of the alkali metal and of the organic halide.

2.-A process which comprises reacting an bydroxyalky] amine base having three hydroxyalkyl groups attached to the nitrogen atom with an alkali metal and subsequently with an organic halide selected from the group consisting of alkyl halides containing at least-four carbon atoms in the molecule, cycloalkylhalides and aralkyl halides; the reaction with the alkali metal and with the organic halide bein'g effected in at least two steps using for each step a part of the stoichiometric quantity of the alkali metal and of the organic halide.

3. A process which comprises reacting one mol of triethanol amine with two mols of an alkali metal and subsequently with two mols of an organic halide selected from the group consisting of alkyl halides containing at least four carbon atoms in the molecule, cycloalkylhalides and aralkyl halides, the reaction with the alkali metal and with the organic halide being effected in at least two steps using for each step a part of the stoichiometric quantity of the alkali metal and of the organic halide. v

RICHARD HU'I'IENLQCHER. 

